Method of coating leather with polymers containing units of acrylyl or methacrylyl dicyandiamide and the resulting article



'tains units of acrylyl or methacrylyl dicyandiamide.

METHOD OF COATING LEATHER WITH POLY- MERS CONTAINING UNITS F ACRYLYL 0R 'METHACRYLYL DICYANDIAMIDE AND THE RESULTING ARTICLE Benjamin B. Kine, Levittown, and Paul "V. MicWherter and Hugo A. Alps, Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application March 21, 1955 Serial No. 495,806

21 Claims. (Cl. 117-76) This invention relates to coated leather products and to processes for producing them. It is particularly concerned with coated leathers having composite multi-layer coatings which have improved adhesion to the leather and to each other and excellent softness and flexibility even under extremes of cold and heat.

U. S. Patent 2,204,520 discloses a procedure for applying aqueous dispersions of emulsion-polymerized acrylic acid esters or the like to leathers. Such dispersions in practice are frequently provided with pigments and are generally covered with one or more final lacquer top coats. The aqueous dispersion serves to fill imperfections and to level the surface of the leather and to improve the adhesion between any lacquer top coats applied and the leather. The coatings obtained from the aqueous dispersions disclosed in the patent provide good adhesion to many leathers and particularly to snuffed, buffed and split leathers. However, on some types of full grain leathers such coatings have poor adhesion. This poor adhesion is particularly noticeable on leathers which have been subjected to certain types of fatliquors, such as sperm oil or cod oil, or which have acquired such a large amount of fatty deposits on the surface of the leather during fatliquoring as to in effect provide a resistance to aqueous coating compositions.

It has now been discovered that improved adhesion may be obtained between the leather and polymers applied to it by means of an aqueous vehicle if the polymer con- In accordance with the present invention, it has been found that the application of aqueous dispersions of resins containing such units to the leather provides improved adhesion to full grain leathers as well as to buffed and split leathers and also improves the resistance to scuffing resulting from rubbing action against the finished leather surface as well as improvement in resistance to wet molding operations.

To impart the improved qualities in the finished leathers in accordance with the present invention, the leather is coated with an aqueous dispersion of a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising 3%to 50% by Weight of at least one monomeric compound having the structure of the following general Formula I:

I CH =C(R) CONHC (=NH)NHCN plication, in the hands of a common assignee, of Hankins,.

Serial No. 495,780, filed on even date herewith. The polymers must not be water-soluble. It is necessary to copolymerize the dicyandiamide monomer with at'least one other copolymerizable monoethylenically un' for preparing the monomeric emulsions before co-' saturated monomer which is of a character that will render the final copolymer insoluble in water. Also, it is preferable from the cost standpoint, and for controlling properties, such as flexibility, to copolymerize the dicyandiamide monomer with more than 50% of one or more less expensive and more readily available co-.

monomers. Preferred compositions of the invention are, therefore, those copolymers of from 5% to 15% of the dicyandiamide monomer or of a mixture of such monomers, the balance of the copolymer being formed of other less expensive comonomers.

Other polymerizable' compounds containing a single ethylenically unsaturated group that may be copolymerized with the dicyandiamide monomer to produce binary, ternary etc. copolymers include the esters of acrylic acid:

or methacrylic acid or the dimer of methacrylic acid with monohydric alcohols such as methyl, ethyl, butyl, octyl, dodecyl, cyclohexyl,,cyar 1oethyl, benzyl, phenylethyl, and the like: diesters'of itaconic acid and the above alcohols; esters of maleic, fumaric, or citraconic acids with the above alcohols; vinyl esters of carboxylic acids such as acetic, propionic, butyric, and the like; vinyloxyalkyl esters such as vinyloxyethyl acetate, etc.; vinyl ethers and sulfides such as ethyl vinyl ether, ethyl vinyl sulfide, butyl vinyl ether, octyl vinyl ether; methacrylonitrile or acrylonitrile; acrylamide, or methacrylarnide, and N-alkylsubstituted amides of these types; vinyl toluene, vinyl naphthalenes, such as 4-chloro-1-vinyl naphthalene, and styrene.

The emulsifiers or dispersing agents that may be 'used polymerization or dispersions of the polymer after polymerization may be of anionic, cationic, or non-ionic type or a mixture of the two types may be used.

Suitable anionic dispersing agents include the higher fatty alcohol sulfates, such as sodium lauryl sulfate, al'

kylaryl sulfonates, e. g. sodium or potassium isopropylbenzene sulfonates or isopropyl napththalene sulfonates,

alkali metal higher alkyl sulfosuccinates, e.g. sodium octyl sulfosuccinate, sodium N-methyl-N-palmitoyltaurate, sodium oleyl isothionate, alkali metal salts of alkylarylpolyethoxyethanol sulfates or sulfonates, e. g. sodium t-octylphenoxypolyethoxyethyl sulfate having 1 to 5 oxyethylene units.

Suitable cationic dispersing agents include laurylpyridinium chlorides, cetyl dimethyl amine acetate, and alkyldimethylbenzylammonium chlorides in which the alkyl group has from 8 to 18 carbon atoms, such as octyl, decyl, dodecyl, or octadecyl, t-octylphenoxyethoxyethoxydimetliylbenzylammonium chloride.

Suitable non-ionic dispersing agents include the following: alkylphenoxypolyethoxyethanols having alkyl groups of about seven to eighteen carbon atoms and 6 to 60 or more oxyethylene units, such as heptylphenoxypolyethoxyethanols, octylphenoxypolyethoxyethanols, methyl octylphenoxypolyethoxyethanols, oxyethanols, dodecylphenoxypolyethoxyethanols, and the like; polyethoxyethanol derivatives of methylene linked alkyl phenols; sulfur-containing agents such as those made by condensing 6 to 60 or more moles of ethylene oxide with nonyl, dodecyl, tetradecyl, t-dodecyl, and the like mercaptans or With alkylthiophenols having alkyl groups of six to fifteen carbon atoms; ethylene oxide derivatives of long-chained carboxylic acids, such as lauric, myristic,

palmitic, oleic, and the like or mixtures of acids such as found in tall oil containing 6 to 60 oxyethylene units 7 per molecule; analogous ethylene oxide condensates of long-chained alcohols, such as octyl, decyl, lauryl, or cetyl alcohols, ethylene oxide derivatives of etherified or esterified polyhydroxy compounds having a hydro-' phobic hydrocarbon chain, such as sprbitan mono'stearate i containing 6 to 60 oxyethylene units, etc also ethylene Patented Mar. 25, 1958.

nonylphenoxypolyeth-' aseaeaa oxide condensates of long-chain or branched chain amines, such as 'dodecylamine, hexadecylamine, and 'octadecylamine, containing 6 to 60 oxyethylene groups; block copolymers of ethylene oxide and propylene oxide comprising a hydrophobicpropylene oxide section combined mer ic esters which have proven to bemost satisfactory are 7 the alkyl esters in which the alkyl group contains one to eightcarbon atoms and whicha-re-exemplified by the following; methyl, ethyl, n-pr'opyl, isopropyl, n-butyl, isobutylfsec-butyl, tert-butyl, isoamyl, t'ert-amyl, hexyl, hept l, fn-oetyL 'and 2-ethy1hi e'xy1 acrylates, methac'rylat'es, and-itaeonates. i

The polymeri'zable emulsions can be prepared at temperatures from C. to about'l00 C., but intermediate temperatures aremuch preferred. Thus, when the preferred co'polymers with esters are made with the esters in which the alltyl group contains one to our carbon atoms a' temperature from aboutl0 'C. to about "60? C; is cmployedfwhereas a-higherftemperature;e. g. 30 C. to 80 is recommended when esters containingfive to eightfcarbon atoms in the alkyl group are copolym'eri'zed. Peroxidic :freeoadical catalysts, particularly catalytic systemsof ahe redox type, are recommended. Such systems, as ;is well. known, are icombinations of oxidizing agents and reducing agents such as a combination of potassium persulfate and sodium metabisulfite. peroxidic agents include the per-salts such as the alkali metal and ammonium :persulfa-tes and perbo'rates, hydrogeniperoxide, organic hydroperoxides such as tert-butyl hydroperoxide and. cumene 'hydroper'oxide, and esters such as tert-butylfperbertzoate. Other'reduc'ing agents include water-soluble thiosulfate's, hydrosulfites, tertiary-amines, such as,;triethanolami-ne,.thiourea, and the salts, such .as the sulfates, of metals which are capable of existing in more than one valence state such as cobalt, iron, nickel, and -coppe'r.., The most convenient method of preparing the. dispersions of copolymers comprises agitating an aqueous suspension or emulsion of the mixture of copolymerizable monomers and a redox catalytic com- Other suitable bination-at-room temperature without the applicationof external heat. The amount of catalyst can vary-but for-purposes of efficiency from 0.01% to 3.0%, based on thewcight of the monomereof the peroxidic agent and the ,same. :orlo'wer proportions of there'ducin'g agent are recommended. In this way, it-is possible to prepare dispersionsiwhich containasxlittle as '1 and as much as or even more of the resinousicopolyn er ona-weigh't basis. It is, however, more-practical, and hence preferred,

to produce dispersions which contain about 30% to 50% resin-solids.

Preferably a pigment -is introduced into the aqueous coatingdispersion and the amount of pigment introduced may vary from that equivalent to about 10% to by weight of the polymer. Generally, the pigment is first dispersed-in water (to a concentrationof' about 30% to 45%) by means of a non-ionic'or anionic dispersing agent or a mixture of both types thereof. Any of. the

alginates ,;ammouium or "alkali metal salts of homopolymers -and copolymersof- -acnylic acid, methac'rylicaci'd;

itaconic acid, maleic acid, fum'a'ric acid, and the'like, such as ammonium .polya'crylate, ammonium salts of copolyl mers of styrene and maleic acid, sodium methacrylate, and soon.

The aqueous dispersion of the polymer or copolymer with or without a pigment dispersed or suspended therein may be applied to the leather at a solids concentration of 10% to 50% (including the Weight of polymer and pigment, if any), equipment such as by brushing, .swabbing, 'or spraying onto the. leather. Afterapplication of the dispersion, it may be dried on the leather either by drying intheambient atmosphere or at somewhat elevated temperatures up to 50 C. The amount of copolymer appliedon the leather varies widely with the type of. leather and the ultimate finish desired. For most purposes, the -amount applied per thousand square foot of the leather may vary from 1 pound to 15 pounds; 7

It is believed that the-improved adhesion obtained on leather by the application ofjthe polymers. containing the dicyandiamido groups is attributable to some chemical or physico-chemicalreaction between :such groups and the .protein molecules of .the leather or with the tanningagent or fatliquor deposit on the leather, or -possibly 01] some joint reaction with two or more of these substances.

However, .it.is vinot intended. that the-invention be limited by any particular theory of operation.

-For some. purposes, the leather product carrying the I single coat'ing, obtained. from. the. application of the aqueous dispersionyof the polymer containing dicyandiamido groups with orl'without. pigment may serve as a suitable finished1product; Forexample, this maybe the case when itis desiredonly to impart a water-repellentsur-face to the...le'ather and the polymerappli'ed by the aqueous dispersionis of highly hydrophobic character as the =result.of.the;.;presence of a long-chain hydrocarbon 'group in'the :com'onomen. However, in many cases, itmay be :desiredatoapplyone or more additional coatings of -a lacquer type'over th'eacoatingobtained from the aqueous polymer dispersion... :Any suitable :lac'q'uer composition may be :applied: such as. those which com su'clras a watel'einsoluhle :soap,;e. g, aluminum stearate,

or various finely-divided silicas, orit maybe colored'with a .white orsuitably colored :pigment. Preferably at least two lacquer top coatings are. applied in succession over the'coating ObifllHQdJflOIH'fthfi aqueous dispersion. When two-such lacquer coatingszare appl-ied, the first is prefer-- ably pigmented-jto augment :the'color and covering obtained by the pigment, if any, applied by:th'e-coatiug. from the aqueous dispersion'gandithe second lacquer coating is preferably-clear orlmerelydulled to .provide the glossi ness orflatness desired in the final 1 surface.

Each of the subsequently appliedcoa'tings should be dried before-any latch-coating is to be .applied and drying maybe --eIfected;as,,-before -either at :normal room temperature in the ambient atmosphere .wor at somewhat elevated temperatures up to 50 C.

If desired, the leather may-be embossed after the coat- 7 ing applied in the aqueous dispersion hasbeendried on theleather andflbefore subsequent lacquerv coatings are applied; or embossing'may be applied at any time. after subsequent coatings are applied 'but preferably before the last or fin'a'l .coatis applied. Such embossing should;

applied. toibe coated .leatherin a dry 1 in 'all,cases,fb'e,

condition. r

As thejv'in'yl or acrylic addition .p01ymer that may. be

:usedffor the 'filrn-forming component o'f'the subsequently I applied lacquer orflacquers, there may be used one or- It may be applied by any suitable aeasaea more homopolymers or copolymers 'of the followingmonoethylenically unsaturated compounds: vinyl 'chlo ride, vinyl acetate, vinyl propionate, vinylidene chloride, esters and nitriles of acrylic and methacrylic acids such as acrylonitrile, methacrylonitrile, and the alkyl esters of acrylic or methacrylic acid in which the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, octyl,

dodecyl, hexadecyl and octadecyl. .Besides the above homopolymers and copolymers, polyvinyl acetals such as polyvinyl acetal itself, polyvinyl butyral or partially hydrolyzed homopolymers and copolymers of vinyl acetate, vinyl propionate or of acrylic and methacrylic esters may be used. Such compounds contain reactive hydroxyl and carboxyl groups. Other polymers containing reactive groups may be used provided the polymers do not contain sutficient reactive groups to render them insoluble in the organic solvent employed. Such polymers include the copolymers containing up to 50 mole percent of S-hydroxyethyl vinyl ether or of B-hydroxypentyl vinyl ether, up to 50 mole percent of aminoethyl acrylate, aminoethyl vinyl ether or N-methylor N-ethylaminoethyl vinyl ether, or up to mole percent of a vinyl pyridine, such as 2-vinyl pyridine, or 4-vinyl pyridine, or of an amide, such as acrylamide, methacrylamide, N-methyl acrylamide, or of an acid, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and the dimer or trirner of methacrylic acid, or the like.

When a plasticizer is'used, it may be a polyester, polyamide, or polyester amide such as may be obtained by the condensation reaction of a dibasic acid with a polyol v More particularly, the plasticizer or a polyamine. (which may be termed a polymeric plasticizer) may be obtained byreacting combinations of materials of the general types noted below:

I Glycols (or other polyols) and dibasic acids 11 Amino alcohols and dibasic acids III Glycols, diamines anddibasic acids IV Glycols, amino alcohols anddibasic-acids V'Amino alcohols, diamines and dibasic acids VI Amino acids, glycols and dibasic acids- VII Amino acids, amino alcohols and dibasic-acids VIII Amino alcohols, glycols and dibasic acids IX Amino alcohols, dibasic acids and hydroxycarboxylic acids ylene glycol, dodecamethylene glycol, 1:l2-octadecanediol and pentaglycol.

Examples of dibasic carboxylic acids are malonic, succinic, glutaric, adipic, fi-rnethyladipic, pimelic, suberic, 1

azelaic, sebacic, undecanedioic, brassylic, isophthalic,

hexahydroterephthalic, p-phenylene-diacetic and acetoner dicarboxylic acid.

Any amino alcohol having at least one hydrogen atom'. attached to the amino nitrogen atom may be employed g. S-aminopentanol-l :6-amino-5-methylhexcarbon atoms; Amino alcohols .which fall withinthis group include ethanolamine 3-aminopropanol, 4-amino-' butan cl, 6- anrinohexano1,.and lO-aminodecanol.

one hydrogen atom attached to each amino nitrogen" atom. The preferred diamines are of formula NH RNH where R represents saturated divalent hydrocarbon radicals with a chain length of at least two carbon atoms, e. g. ethylenediamine; hexamethylenediamine, 3-methylhexamethylenediamine, and decamethylenediamine. However, aromatic diamines such as m-phenylenediamine may also be used.

Any polymerizable monohydroxy monocarboxylic acid or ester-forming derivative thereof may be employed. The preferred hydroxy-acids are of formula HO'RCOOH where R represents saturated divalent hydrocarbon radicals, e. g. d-hydroxycaproic, IO-hydroxydecanoic, and 12- hydroxystearic acid.

Any polymerizable monoaminomonocarboxylic acid or ester-forming derivative thereof may be employed including 6-aminocaproic, 9-aminononanoic, and ll-aminoundecanoic, and lZ-aminostearic acids, caprolactam, etc.

The organic solvents that may be used include ketones such as acetone, methyl ethyl ketone and dioxane; hydrocarbons such as xylene, toluene, benzene as well as parafiinic ornaphthenic types such as solvent naphthas, esters chrome orange, phthalocyanines, such as copper phthalocyanine, titanium dioxide, lithopone, chrome yellow, ultramarine blue, red cadmium, yellow cadmium, organic toners and lakes, and so on.

It has been found that the adhesion between the leather and the coating thereon, especially when several layers 1 are applied to the leather, is even further improved when a polyisocyanate is applied to the coated leather at any time after the aqueous polymer dispersion has been dried on the leather. For example, the polyisocyanate may be applied lacquers or it may be applied to the dried coated coating obtained from the aqueous dispersion. It may also be applied as a component in any of the subsequently applied lacquers or it may be applied to the dried coated leather after any of the-subsequently applied lacquers. Preferably, if a polyisocyanate is employed, it is incorporated in the first lacquer coating applied over the polymer coating obtained from the aqueous dispersion.

Examples of the polyisocyanates that may be employed toluene 2,4 diisocyanate, 4,4 diisocyanato biphenyl, 3,3 dimethyl 4,4 diisocyanatobiphenyl, and 3,3 dimethoxy 4,4 diisocyanato biphenyl. The polyisocyanates have various reactivities, some being much slower than others. For example, diphenylmethane-4,4-diisocyanate is highly reactive whereas the 3,3-dimethoxy-4,4-diisocyanatobiphyl is relatively slow. i To compensate for the difference in reactivity, the pro-. portionadded may be increased for the slower ones and decreased for the faster ones or basic catalysts, such as tertiary amines may be included, especially with'the slower ones. .Mixturesof the polyisocyanates may be used of V which preferred combinations are mixtures of toluenei 2,4-diis'ocyanate with either 3,3-dimethyl-4,4-diisocya 4:4":4"-triisocyanate and dipheny1-2;4:4 triisocyanate,

that the drying of the polyisocyanate in place on the coatedleather shouldnot be-so prolonged or at such high temperatures: that all the isocyanate groups are oompletel y reacted. By so leaving the active isocyanate groups the" drying of subsequent lacquer coatings provides the op portunity for reactive combination of isocyanate groups with any reactive groups that may be present in such subsequently applied lacquers;

It. appears that, whena polyisocyanat'eis"used-theimproved adhesion between the several layers of the coating and between the leather is at least partially-attribute ble to some: reaction. between the polyisocyanate; the leather, the film-forming component and-possibly the plasticizer in the several coatings". It should 'be under-- stood, however, that. the application to the leathei of" the aqueousdispersionsof the dicyandiamidopolymers imparts improved adhesion between lacquercoatings and the leather'ancl shows. some improved-adhesion between thexleather and the polymer depositedfrom the aqueous dispersion. This adhesionisfor most purposes fully adequate even without the employment of a polyisocyanate. The application of the pol-yisocy'anate,- however, may be desirable to obtain even better adhesion for some particular purposes and has also the advantages ofincreaeing the dryness or slipperiness. of the top surface'of the coated leather- When two lacquer coats are applied over the coating. obtained frorn the aqueous polymer dis persion, the first of such lacquerspre-f'erabl-y has the following composition: from to 200- parts-by wei'ght of plasticizer, if present, per 1:00 parts of the addition.

polymer or cellulose ester; from 5m: l50*'partsby weight of a pigment or mixture of pigme'nts per 100 parts of the fihmforming component; from-1% to" 65% by weight of a polyisocyanate; if used', this percentage being based on the sum of the Weights of the pla'sticizer and film-forming component. The amount of solvent employed may be such as to provide a solids concentration (that is materials other than the solvent themselves) of 2% to 20% by weight. The final lacquer coat is usually an unpigrnented solution (either clearer dulled by an inert. delustering' filler) of the pl asticizer and film-forming component, either or both of which may be the same as or ditterent from. the respective plasticizer and filmforming component of the first lacquer coat. When both lacquer coats contain plasticizer; the proportion in the final coating is somewhat les'sinproportion to the film-- forming component than the proportion usedin the first lacquer coating. Generally, it iswithin the proportion of 15 to '80 parts per 100 parts of the film-forming component- In the following examples, which are illustrative of theinvention, parts and percentages are by weightunless otherwise specified:

Example 1 (a) A dispersion of a copolymer was prepared by emulsifying. 97 parts by weight of ethyl acrylate with 3 parts by weight of acrylyl dicyandiamide in about 300 parts by weight of water with about 2 parts by weight of sodium l'auryl sulfate and 6 partsby weight of an ethylene oxide condensation product of an octyl phenol containing between 30 and 50 oxyethylene units per molecule. To the emulsified monomers 0 .3%by "weight of ammonium persulfate, 0.06% of; sodium hydrosulfite, and 1% u-iethanolamine'were added to catalyze the copolymerizat-ion. whichiwas carried out for a period of about fifteen minutes during which the temperature rose from 20 C. to 45- C. i

(b); Nine parts of red iron oxideare 'diSPGISEidLlLl 14- parts of Water by" means of two: parts of a suitable dispersing agent, such as a; mixture of: equal parts of sodium. 1 lauryl sulfate: and, t-oetylphenoxypolyethoxw ethanol eontai nirrg'about 10 oxyethylene units in com-- binationwith partof a suitable protective colloid, such as methyl cellulose, and'the mixture was added to lOo'partsof the-copolyme r-dispersionof part (a) hereof. The resultingpigmented dispersion was swabbedon several pieces ot a iullgrain upholstery leather and dried at 50 C. The coating exhibited excellent adhesion to the leathers.

- (e) The procedures of parts (a) and (b) hereof is repeated except the .acrylyl dicyandiamideis omitted so that a dispersionrof ahomopolymer of'ethylacrylate is produced and applied to the full grain' upholstery leather. The coating on therleathercould-be pulledolfthe leather intact. I

Example 2 (a) A' mixture of40 parts of red iron. oxide, six parts of a lasticizer consistin'g of a polyester obtained by the reaction-of sebacic aeid'wi-th'an excess ofpro'pylene glycol and llavin'ga number averageimolecular Weight of about 4,000; 2.9- parts by weight of a copolymer of 90% vinyl chloride and 10% vinyl. acetatehavin'g a number average molecular weight of about 40,000, 6.1- parts ethoxyethyl acetate, 25 parts of methyl'ethyl ketone' and 20 partsof a petroleum solvent consisting of a mixture of aromatic, naphthenic', and' aliphatic hydrocarbons is ground in a ball mill'for Z t'hours toform a pigment dispersion.

(b )-A"solution'is"also formed-from 3.l parts of the same 'pl'asticizer' as above and 5 .0 parts of the same vinyl copolytner in '10 parts o't'ethoxyethyl acetate. 44 parts of methyl ethylj ketorie'and 3419 parts of a hydrocarbon solvent largely consisting of 'xylol'.

(0)"Th' solution ofpa'rt (5) hereof is then mixed with the milled pigment dispersion of part (a) hereof in the ratio; of 90 partsot the; former to 1.0 parts of the latter. The resultingdispersionf is applied to a piece of the coated leather obtained in part (b) of Example 1- hereof and dried'at '50 C; forabout-three hours.

(d) Then" aclear coating: is applied to the coated leather obtained 'inpart ('c) hereof by spraying a solution containing about 1.5% of the same plasticizer (of part (a)) and 5% of the same'vinyl copolymer (of part (a)) in a solvent mixture, composed of 10% of ethoxyethyl acetate, 55% methyl ethyl ketone and 35% of a hydrocarbon composed largely of Xylene. After applying the clear coating by spraying, it was dried at 50 7 C. The final coated leather had a glossy color and was soft and flexible.

7 Example 3 i (a) The procedure of Example 2, parts (a) through (d) isrepeated' except that 3.0- parts of tQIuene-Z'A-diisocyanateis added'to the solution of part (b) thereof. The resulting leather has a drier feel, shows excellent adhesion betweenthe'coatings' and also between the leather and the several' -coating's', and is even more resistant to wet'mol'ding operations than that obtained without the diisocyanate in Example 1'.

(b) The procedure of Example 2, parts a) through (d'). is repeated except that 3.0 parts of toluene'2,4- diisocyanate is addedto the solution of part (b) thereof and the dispersion obtained in part (c)- thereof is app'lieditothe leather obtained" in part (0') of Example 1 wherein the full grainupholstery leather is coated with a homopolymer' of ethyl acryl-at'e. The adhesion of the coatings to theleather is fair but special precautions areneeded? during "wermolding operations to prevent damage to the finished leather.

. 7 Example 4 (a); Theiprocedure is repeated exeeptwthat the monomers: are replaced with partszb'y weight of' ethyl acryla'te; 1 5 parts by weight of n-butyl aerylate and-5 parts of .acryIyl dicyandiamidc.

ofi Eit'arnple 1, parts" (a) and (1)),v

The dried leather showed excellent adhesion between it self and the coatings.

(b) To the coated leather obtained from part (a)' hereof there is applied two lacquer coatings of the same composition as and by the procedure of parts (a) through (d) of Example 2. Excellent adhesion is obtained between the lacquer coatings and the leather.

Example (a) The procedure of part (a) of Example '4' is repeated except that the five parts of acrylyl dicyandiamide are replaced with five parts of methacrylyl dicyandiamide.

Good adhesion of the coating to the leather is obtained.

.(b) The coated leather obtained in part (a) hereof has applied to it the two lacquer coatings of parts (a) to (d) inclusive of Example 2, the application being made by the procedure of Example 2.

Example 6 (a) An aqueous dispersion containing 20% of a copolymer of 40 parts by weight of methyl acrylate, 50 parts by weight of n-butyl acrylate, and 10 parts by weight of methacrylyl dicyandiamide is pigmented as in Example 1(b) except the red iron oxide is replaced Example 7 An aqueous dispersion containing 20% by weight of a copolymer of 15 parts by weight of methyl methacrylate, 70 parts of n-butyl acrylate, and 15% of acrylyl dicyandiamide is applied to a full grain leather in the manner described under Example 1, parts (a) and (b) after pigmenting according to that procedure.

Example 8 An aqueous dispersion containing 30% by weight of a copolymer of 72 parts of butoxyethyl acrylate, 21 parts styrene, and 7 parts by weight of acrylyl dicyandiamide is pigmented and applied to a full grain leather in the manner described in Example 1, parts (a) and (b).

The application of an aqueous dispersion of a polymer to a leather for the purpose of coating it avoids excessive impregnation of the leather which sometimes occurs when a polymer is applied from an organic solvent solution thereof. It therefore, avoids the stiffening and the undesirable break and feel of the coated product that are caused by severe impregnation. At the same time, the application of the aqueous dispersion of the polymer has the advantage of enabling the operator to apply the composition containing a large proportion of solids therein without encountering the disadvantages of high viscosity and low mobility which would be encountered if the polymer were applied by the use of an organic solvent solution. In addition, the application of the particular polymers of the present invention by an aqueous dispersion provides improved adhesion for many types of leather, particularly those which have a large amount of fatty deposits on the surface of the leather as a result of the fatliquoring operations. ings are applied over the coating applied from the aqueous dispersion of the particular polymers of the invention, improved adhesion is obtained between the lacquer top coating system and the leather as compared to that obtained with polymers heretofore suggested to be applied by aqueous dispersion which contain no dicyandiamide units.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

When lacquer top coat-.

Weclaimz- 1. As an article of manufacture, a leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising 3% to 50% by weight of at least one monomeric compound selected from the group consisting of acrylyl and methacrylyl dicyandiamides.

2. As an article of I'manufacture, a leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising 5% to 15% .by weight of acrylyl dicyandiamide. 3. Asan article of manufacture, a leather having a coating thereon comprising a water-insoluble linear polymer of j monoethylenically unsaturated molecules comprising 5% to 15% by Weight of methacrylyl dic'yandi amide.

4. As an article of manufacture, a leather having a coating thereon comprising a Water-insoluble linear polymer-of monoethylenically unsaturated molecules comprising'80% ethyl acrylate, 15% n-butyl acrylate, and 5% by weight of acrylyl dicyandiamide.

5. As an article of manufacture, a leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising ethyl acrylate, 15% n-butyl acrylate, an 5% by weight of methacrylyl dicyandiamide.

6. As an article of manufacture, a leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising 97% of ethyl acrylate and 3 of acrylyl dicyandiamide. I

7. As an article of manufacture, a leather having a 3 multi-layer coating thereon, one layer of which comprises 1. a pigmented water-insoluble linear polymer of1mono+ ethylenically unsaturated molecules comprising 3% to 50% by weight of at least one monomeric compound selected from the group consisting of acrylyl and methacrylyl dicyandiamides, and, superimposed on said layer, at least one lacquer coating comprising a film-forming component.

8. As an article of manufacture, a leather having a multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of monoethylenically unsaturated molecules comprising 3% to 50% by weight of at least one monomeric compound selected from the group consisting of acrylyl and methacrylyl dicyandiamides, and, superimposed on said layer, two lacquer coatings the first of which is pigmented.

9. As an article of manufacture, a leather having a multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of about 5% to 15% by weight of acrylyl dicyandiamide, and, superimposed on said layer, a pigmented lacquer coating comprising a vinyl resin and a plasticizer for the vinyl resin.

10. As an article of manufacture, a leather having a multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of about 5% to 15% by weight of methacrylyl dicyandiamide, and, superimposed on said layer, a pigmented lacquer coating comprising a vinyl resin and a plasticizer for the vinyl resin.

11. As an article of manufacture, a leather having a multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of about 5% by weight of acrylyl dicyandiamide, 80% of ethyl acrylate,

on said layer, a pigmented lacquer coating comprising a vinyl resin and a plasticizer for. the vinyl resins =13. As an article of manufacture, a leather having a multi-layer coating thereon, one. layer of which comprises a pigmented water-insoluble linear polymer of about by weight of acrylyldicyandiamide and about 95% of ethyl acrylate, and, superimposed on said layer, a pigmented lacquer coating comprising a vinyl resin and a plasticizer for the vinyl resin.

14. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising 3% to 50% by weight of "at least one monomeric compound selected from the group consisting of acrylyl and metha'crylyl dicyandiamides, and then drying the coated leather.

15. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of about 5% of acrylyl dicyandiamide,

80% of ethyl acrylate, and 15% of n-butyl acrylate, and

then drying the coated leather.

16. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of about 5% of meth'acrylyl dicyandiamide, 80% of ethyl acrylate, and 15% of n-butyl acrylate, and thendryin'g the coated leather.

one or saiddispersion and lacquer beingpi mented, and drying the lacquer.

19. As an article of. manufacture, a full=grain-leather having a coating thereon comprising a waterdnsoluble linear polymer of monoethylenically unsaturated mole- V cules comprising 3% to 50% by Weight of at least one 17.. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble monomeric compound selected from'the group ct'insistin'g of acrylyl and methacrylyl dic'yandiamides';

20. As an article of manufacture, a full-grain leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically" unsaturated melecules comprising 80% ethyl acrylate, 15% n butyl anylate, and 5% by weight of nie'thacrylyl dicy'andiafnide.

21. The method of finishing full-grain leather compris ing applying thereto an aqueous dispersion of a Waterinsoluble linear polymer of monoethylenically unsaturated molecules comprising 3% tot% by weight of at least one monomeric compound selected from the group consisting' of acrylylan'd' methac'rylyl dicyandiamides; and

then drying the coated leather.

References Cited in the file of this patent UNTIED STATES PATENTS 2,204,520 Walker et al. a e- June 1 1-, 1940 2,407,161 Kaiser etal. Sept. 3, 1946 2,430,479 Pratt et 211. -i.- Nov. 11, 1947 Hughes e Nov. 16, 1954 OTHER REFERENCES Hackhs Chem. Dic., 2nd ed., page 19. 

18. THE METHOD OF FINISHING LEATHER COMPRISING APPLYING THERETO AN AQUEOUS DISPERSION OF A WATER-INSOLUBLE LINEAR POLYMER OF MONOETHYLENICALLY UNSATURATED MOLECULES COMPRISING 3% TO 50% BY WEIGHT OF AT LEAST ONE MONOMERIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ACRYLYL AND METHACRYLYL DICYANDIAMIDES, THEN DRYING THE COATED LEATHER, APPLYING THERETO A LACQUER, AT LEAST ONE OF SAID DISPERSION AND LACQUER BEING PIGMENTED, AND DRYING THE LACQUER. 